CN108014021A - A kind of tooth filling renovation material and preparation method thereof - Google Patents
A kind of tooth filling renovation material and preparation method thereof Download PDFInfo
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a kind of tooth filling renovation material and preparation method thereof, belong to dental material technical field.The tooth filling renovation material of the present invention includes resinous substrates, auxiliary agent, filler and pre-polymerization resin powder；Wherein, pre-polymerization resin powder is polymerized by Bis GMA (Bisphenol A-glycidyl Methacrylate).The preparation method of tooth filling renovation material of the present invention includes the following steps：Prepared by pre-polymerization resin powder, resinous substrates are mixed with auxiliary agent, mixture A is mixed with filler, mixture B is mixed with pre-polymerization resin powder.The tooth filling renovation material that the present invention is prepared, the bending strength after curing are 80 120MPa, and compressive strength is 200 300Mpa, shrinking percentage is 1.3~2%, product mechanics high comprehensive performance compared with prior art, shrinking percentage is low, suitable for industrial mass production.
Description
Technical field
The invention belongs to dental material technical field, more particularly to a kind of tooth filling renovation material and preparation method thereof.
Background technology
1. on dental cases
1.1 dental disorder
As human society life mode changes and social population's aging, teenager's dental erosion and the elderly's tooth
Heel of tooth dental caries incidence rises year by year.At present, incidence of the dental erosion in teenager is up to 60%, epidemiology survey
Researches show that the incidence of Beijing university crowd is 45.8%.Investigated and reported according to Third National oral health epidemiological
Accuse, the dental caries in old people rate of China 65-74 Sui is 98.4%, and wherein cementum caries illness rate is up to 63.6%.This hard group of two classes tooth
Inflammation in pulp inflammation and local jaw can be caused by knitting disease and further developing, and even resulted in loss of tooth and pulled out, and chew work(
It can lose.With the development of disease, patient is subjected to more physiological pains, and since disease middle and advanced stage treatment difficulty increases
Add, treatment cost increase, the medical burden of patient and country aggravates, and therapeutic effect declines compared with disease early stage on the contrary.
Almost monopolized currently for the filling reparation product of acid corrosion by external product, these product prices are high, greatly
The big medical burden for adding patient.Restraining factors of this kind of material in terms of materialogy are mainly matrix and filler refractivity
Match somebody with somebody, enamel refractivity matching, as close possible to human enamel's mechanical strength the problem of；It is domestic few for the prevention product of cementum caries
There are the filling repair materials that acid corrosion of the research and development with independent intellectual property right suffers from tooth and the prevention ＆ protection material that cementum caries suffer from tooth, it is right
In improving patients ' life quality, the economic guidance of patient and country is reduced, there are larger economic results in society.
Tooth erosion disease is due to that acidic materials are acted on caused by facing.Although tooth erosion disease is a multifactor disease
Disease, research show that teenager's dental erosion is inseparable with a large amount of frequently reference sodas.American-European countries's tooth erosion disease is suffered from
Sick rate is differed from 20% to 71%, and incidence of China's tooth erosion disease in blue or green few face may be up to 60%.For tooth erosion disease, mesh
It is preceding to be also applied to clinical early diagnosis technology without ripe.It is most of to tooth erosion disease patient, only when enamel
There is demineralization and the performance of defect, hospital's medical treatment of just coming.At present to the early treatment of tooth erosion disease with demineralization enamel remineralization/
Based on enhancing and enamel defects recovery technique.
Enamel is tissue most hard in human body, and main component is hydroxyapatite, and larger resistance is worn away to chewing.
Enamel has the optical property (transparency, translucence and opalescence) of uniqueness at the same time so that tooth have certain gloss and
Texture.Hydroxyapatite crystal influences the scattering of light in enamel, and the different enamel fiber in direction is reflected and dissipated at different angles
Penetrate light so that enamel and color of teeth performance are different.Material currently used for enamel defects reparation is mainly resin base reparation
Material and ceramic-like repair materials, wherein, due to easy to operate, physicochemical property is superior for resin base repair materials and recovery technique,
And color and luster selects the features such as flexible, it is widely used in the clinical reparation for carrying out enamel defects.
2. on resin matrix
2.1 resin brief introductions
From the sixties in last century resin base repair materials enter dental restorative area since, composite resin material performance obtains
Grow rapidly.Compound resin is acrylic resin (such as Bis- for the inorganic filler and difunctional for having specially treated
GMA the polymer composite) mixed, is cured, usually at normal temperatures by means of chemistry initiation system or light initiation system
Matched with resin base adhesive system.The main component of compound resin is polymerized monomer, inorganic filler, activates diluent, is poly-
Close reaction initiator, accelerating agent and some auxiliary agents etc..Polymerized monomer is the acrylic ester compound of difunctional, constitutes tree
The main component of aliphatic radical matter, commonly uses bisphenol-A-bis- (3- methacryloxy -2- hydroxypropyls) ether, i.e. Bis-GMA.It is common
Inorganic filler has а-quartz, silica, glass dust, porcelain powder, bead etc..Inorganic filler is used to improve composite resin material
Mechanical strength, reduces thermal coefficient of expansion, its dosage is about the 50-85% of compound resin overall weight.Compound resin after curing
Material has preferable bio-safety performance and physical mechanical property.Composite resin material can be deployed into various according to clinical requirement
With tooth similar in color and luster, the color and luster of natural teeth can be simulated to a certain degree.
Current compound resin product still suffers from certain deficiency：1) there is volume contraction during compound resin monomer cure,
May be not closely sealed with hole wall, cause Micro blazed-grating or secondary caries；2) it is still compound since material abrasion causes anatomic form to be lost
Resin dummy common problem；3) optical index of compound resin and the tooth of people still suffer from certain difference, cause to repair
Multiple material has macroscopic line of demarcation with dental interface, influences beauty.For compound resin, how mechanicalness is further improved
Can, reduce condensation and shrink, strengthen aesthetic properties, be the key issue of domestic and foreign scholars and material scholar concern.
The progress of 2.2 dental prosthetic materials --- light-cured composite
Light-cured composite resin for oral cavity is ripe at present by the development of nearly 40 years since the 1960s comes out
Commercially produced product also have more, but the property of this resinoid is also defective in some aspects, as wearability and elasticity modulus it is low,
Adaptation is poor, do not have X-ray resistance and filling treatment after tooth with irritation, therefore also need to further improvement and
Modified, current research work is concentrated mainly on two aspects of resin monomer and filler.
(1) research of new main monomer
Light-cured composite resin for oral cavity is a kind of new composite material proposed by Bowen earliest, he is by Bis-GMA
As reisn base material, prepared compound resin performance is greatly improved compared with PMMA, is widely used in oral cavity restoration field.But
Bis-GMA viscosity is too big, and hygroscopicity value is higher, cure shrinkage is bigger than normal, and therefore, people synthesize newly in research all the time
Main monomer, it would be desirable to obtain the more excellent reisn base material of property.
Due to the effect of intermolecular hydrogen bonding, the viscosity of Bis-GMA reaches 1200Pas, this is unfavorable for matrix and inorganic filler
Mixing.Matrix viscosity generally is reduced by adding diluent, but the addition of diluent often improves the hygroscopicity value of resin
And cure shrinkage.
(2) study on the modification of conventional fillers
The species of filler, granularity, size distribution, refraction index, hardness, X-ray resistance and in compound resin it is shared
Volume mass percentage can influence performance and the clinical manifestation of compound resin.In addition, in order to improve filler and polymeric matrix
Combination power, generally all filler is first passed through in advance silanization treatment or other surfaces processing, to improve the boundary between filler and matrix
Face combines, and improves wear hardness.
(3) research of new diluent monomer
Research for new diluent monomer, is mainly the desire to prepare that cure shrinkage is small, curing degree is high (with double bond
Conversion ratio judges) and will not reduce the monomer of compound resin mechanical performance.
(4) exploitation of novel nanometer functional filler
In the filler that dentistry uses, since the X-ray resistance of resin material is weak, without bright between carious tooth tooth body
Aobvious contrast, when secondary caries occurs, X-ray on piece is difficult to bedding material, hole lining material or filler and secondary caries progress
Differentiate.
(5) light-cured composite resin for oral cavity in the application there are the problem of
Clinically the use of compound resin is relatively broad at present, but common resin still suffers from some problems and defect,
It is mainly shown as：Elasticity modulus and (with the silver amalgam ratio) filler or reinforcing material and resin using more high rigidity that wear no resistance
The combination power of matrix, can improve the property of this respect；There is plup stimulus symptom after filling treatment, the reason is that cure not exclusively,
Residual monomer polymerization exotherm；Easily trigger secondary caries, because volume contraction during resin polymerization, thermal coefficient of expansion is mismatched with tooth；
Do not have X-ray resistance.
2.3Bis-GMA/(SiO2-ZrO2) nanocomposite preparation and performance study
Modern society, the use of new material play immeasurable effect, oral cavity doctor during social development is promoted
Development is same, and the progress of science of dental materials each time can all promote Oral Science to stride forward major step, it may be said that
There is no the development of science of dental materials just without the progress of modern Oral Science.At present, dentistry composite resin matrix monomer is commonly used
Have：A kind of is the matrix methyl methacrylate for being initially applied to Walter Bauer nineteen thirty-sevens by German artificial tooth making
Resin (MMA)；Other two kinds are to be made by U.S. dentist Bowen RL in invention in 1956 with epoxy resin (Epoxy Resin)
For dental resin matrix, and in the Bisphenol A-glycidyl Methacrylate (Bis-GMA) of synthesis in 1962 it is used as dentistry tree
Aliphatic radical matter.
With the use of methyl methacrylate clinically, what it was exposed has larger polymerization shrinkage, higher
Thermal coefficient of expansion, it is easy to change, have infringement to dental pulp, easily formed secondary caries the shortcomings of be gradually found.Since invention is with double
Since phenol A glycidyl Methacrylates (Bis-GMA) resin is matrix, MMA progressively instead of with the performance that its is excellent.
At present, it is most commonly used be using diluting monomer be double methyl methacrylate triethylene glycol ester (TEGDMA) as diluting monomer,
Bis-GMA is added to collectively as matrix resin.In matrix resin, while TEGDMA plays dissolution and dilution, also
Play the role of cross-linked polymeric, improve the performance of compound resin.
Compound resin main component is resinous substrates and inorganic filler, the wherein species of inorganic filler, quantity, particle diameter distribution
There is important influence Deng the properties to material, the main density for influencing composite material, tensile strength, hardness, toughness and
Mechanism etc..The interface performance that composite material is improved using the method for surface treatment is feasible way.Nano filling is strengthened compound
The exploration of material, is always the research emphasis of composite material educational circles in the latest 20 years.
2.4 high strength resin dental materials and preparation method thereof
Existing frequently-used dental resin material is mainly gathered by methyl methacrylate monomer and MPM methyl polymethacrylate
Conjunction forms, and resin tooth and resin dental base acrylic resin powder base material etc. are used as in dentistry；The material is not wear-resisting in use, intensity and
Shade deviation, easy yellowing, frangibility；The combination of acrylic resin tooth and acrylic acid denture base resin is also poor, the phenomenon easily fallen off；
" gold disclosed in " resinous composition for dental use " disclosed in China Patent Publication No. CN1196923A and Publication No. CN1210713A
Belong to reinforced composite resin " in the case of no addition trace rare-earth element, similarly there are similar problem.
2.5 nano fluorine-containing resin dental materials and preparation method thereof
Modern dental material generally uses polymerizable monomer, and most is methyl acrylic ester with inorganic filler and polymerizeing
The composite material that initiator is formed.After Rafael L.Bowen invent BisGMA monomers, this kind of material obtains rapidly
Development, at present, be widely used in dental filling material, crown, Dian Qiao, admixture, inlaid material, outer edge material and artificial tooth
With the repairing of baking-ceramic tooth etc..But as people gradually deepen the understanding of oral cavity material, dental material requirement is got over
Come higher.Not only requiring nothing more than it has the function of that specific intensity etc. uses, but also requires it to resist thin with bioactivity
Bacterium, anti-tooth dental caries, therefore multi-functional resins material just becomes the direction of new-product development.It is only this more in following market
The material of function can meet the needs of people.
Many researchs have confirmed, if the material of tooth filling has the ability of release fluorine ion, obturation edge
Secondary caries significantly reduces.Itself main reasons is that：The fluorine ion that material is discharged can be diffused in the sclerous tissues of adjacent teeth
Go, and combined with the hydroxyapatite in tooth body, so as to improve the anti-caries bad ability of hard tooth tissue.In long-term clinical research
Found in practice, in the repairing of the 5th class tooth dental caries, if dentine has minute crack, using Glass ionomer cement, occur after
Send out the phenomenon of the dental caries compound resin not fluorine-containing far less than exclusive use.The reason is that the former can discharge fluorine ion, improve
The anti-caries ability of tooth.Due to the poor compatibility of fluorinated inorganic salt and resin matrix, being introduced into compound resin to cause
The performance depreciation of the mechanics of materials.
The throwing rotary light performance and wearability of compound resin can be significantly improved using nanometer powder, but nanometer powder exists
Self assemble, can significantly affect the flow behavior and clinical manipulation feel of material, cause material flowing deformation unstable, i.e., material sticks
Degree can change with the operating time.Importantly, this self aggregation behavior can cause powder skewness in resin matrix
Even, caused nanometer powder accumulation regions can become originating point or the region of stress cracking.Therefore, dispersing nano powder well
It is very important making link.Existing dispersion technology is ground including three beaming rollers, and sonic oscillation, and Pneumatic high-speed disperse, but
It is uneconomical efficient.
The preparation method and applications of the gear division compound resin of 2.6 PMDM containing function monomer and modified hydroxylapatite
Later stage the 8's 0 of 2nd 0 century, authoritative periodical once optimistically foretold that dental caries can be controlled and are likely to become
The disease of another kind disappearance.But this judgement is not supported in the investigation of World Health Organization's right pop disease, and statistical result shows,
The illness rate of dental caries remains high in some undeveloped countries.The caries prevalence rate per capita in China is 40% at present, and wherein children suffer from dental caries
Rate is 80%, and young people's caries prevalence rate is 60-70%, and dental caries in old people rate is 52%, and each patient is averagely related to 2-3 tooth,
Tooth is also 70% with scorching and periodontitis illness rate.The wilderness demand indication gear division filler of oral cavity gear division filler has huge
Market prospects.Traditional compound resin refers to one kind by organic resin matrix and inorganic filler and triggers system to be composed
Teeth repairing material, be that the restoration of tooth for substituting silver amalgam treats essential important materials, be widely used in
The directly or indirectly repairing and treating of all kinds of defect of teeth.
Preferable compound resin used for stomatological repair should have higher mechanical strength, and thermal coefficient of expansion is similar to tooth,
Less polymerization shrinkage, certain caking property, polishing performance is good, insoluble in saliva, the advantages that color and luster is close with tooth.But mesh
It is preceding both at home and abroad, especially the compound resin of domestic production still suffers from larger problem in some aspects, as compound resin intensity compared with
Silver amalgam is low, and polymerization shrinkage is big etc..In recent years, as doctor and sufferer are to simplifying the requirement of medical procedure on mouth step increasingly
Enhancing, requirement of the people to performance of oral cavity resin for restoration itself are also higher and higher.Traditional resin for restoration does not have caking property, when it
It is filled in tooth when playing repair, if do not aided in binding agent, will be easy to produce microleakage.So research
Develop inexpensive efficient gear division compound resin and have important clinical meaning, but it is domestic at present with independent intellectual property right and inexpensive
Gear division compound resin is relatively fewer, and Clinical practice is mostly import gear division compound resin, and the product of domestic brand is less, but also all
Respectively there is excellent, shortcoming, there is no a kind of product of high comprehensive performance.
2.7 dental materials, dental material composition, dental prosthetic material and solidfied material
In the past, using characteristics such as its good curability and the transparencys, the free radical using (methyl) acrylate as representative
Polymerizable monomer widely uses in the various fields such as coating, plate making, optical material and dental material.
Wherein, in dental material field, the tooth that is used in the reparation be widely used in the carious tooth of natural teeth, fracture etc.
The dental prosthetic materials such as section's compound resin, for making the various dental adhesives of dental compound resin and tooth bonding,
And artificial tooth, dental plate material etc..
Dental compound resin is generally made of polymerizable monomer, polymerization initiator and filler, as polymerizable monomer, from
From the viewpoint of mechanical strength, wear resistance and aesthetics of security, solidfied material in organism etc., radical polymerization is used
Multifunctional (methyl) acrylate of property.As multifunctional (methyl) acrylate, double (4- (the 3- methacryls of 2,2- are used
Epoxide -2- hydroxy propyloxy groups) phenyl propane (common name Bis-GMA), dimethacrylate 2,2,4- tri-methyl hexamethylenes are double
(2- carbamoyloxies ethyl) ester (being commonly referred to as UDMA), particularly Bis-GMA were proposed in tooth first since 1962 by Bowen
Since application in section's material, the polymerizable monomer still as almost all of dental compound resin uses now.
However, for dental compound resin, pointed out from clinical sites, the bending strength of solidfied material, elasticity modulus and
It is raising, water suction and the reduction of color-shifting colorant of wear resistance, the reduction of polymerization shrinkage when curing, same with natural teeth saturating
The improvement leeway of bright property and aesthetics etc. is big.Particularly polymerization shrinkage can cause because dental compound resin from bonding plane shell
From and the generation of shrinkage joint that generates, become secondary caries, the reason for plup stimulus, coloring, restoration come off etc., therefore strong uncommon
Prestige is reduced as far as.In addition, in order to meet the high request to aesthetics, and x-ray imaging is assigned, it is compound in dental
The filler of high index of refraction is commonly used in resin, it is therefore desirable to imparting and the transparency similar in natural teeth, it is desirable to which used is poly-
The high refractive index of conjunction property monomer.And then from from the viewpoint of intraoral durability (impact resistance and broken resistance), it is desirable to
With high bending strength.
Reduction for polymerization shrinkage, it is proposed that gathered using open loop of the polymerization shrinkage usually than acrylic compounds smaller
The epoxide of conjunction property, oxetane compound (Hu Xiaogang etc., the research of dental prosthetic material-light-cured composite
Progress, material Leader, 2006,20 (5), 44).By using these compounds, there is a tendency that can reduce polymerization shrinkage, but because
Curing system is different, so the problems such as needing dedicated priming paint (primer) is also very much.In addition, the sight from aesthetics and operability
It is problematic from the point of view of point.
Polymerization shrinkage (Zhang Dongqing etc., Bis-GMA/ (SiO2- is reduced in addition, it is also proposed and improve the loading of filler
ZrO2) preparation of nanocomposite and performance study, Chinese medicine physics magazine, 2014,31 (3), 4957；Li Xiaodi,
High strength resin dental materials and preparation method thereof, publication number CN1456142A).However, the because shrinking percentage of monomer used
Greatly, so its effect is limited.
It also proposed low-shrinkage material (Ma Rongtang, Yan Gang, Yan Pengtao, the Xie Qi using siliceous (methyl) acrylate
It is thrifty, nano fluorine-containing resin dental material and preparation method thereof, 101721316 A of publication number CN).However, the synthesis of the material is numerous
It is trivial, leave problem in industrial manufacture view.It is in addition, problematic from the viewpoint of the mechanical strength of solidfied material.
Accordingly, it would be desirable to have a kind of polymerization shrinkage when can be used for dental prosthetic material, cure it is small, industrially also can be with
The polymerizable monomer of cheap price manufacture.
A kind of 2.8 preparation methods of new light-cured composite resin for oral cavity material
Dental composites are that last century middle nineteen sixties occur as Molar repair material.It is in recent years, multiple
Resin have developed rapidly, its application is also more and more extensive.
What compound resin was mainly combined together to form by organic resin matrix and inorganic filler, it is general main comprising four
Part：(1) organic substrate, organic substrate mutually by polymerisable monomer system, the light initiation system of Raolical polymerizable can be triggered
Also extend the composition such as stabilizer of compound resin storage life；(2) inorganic filler, generally glass dust, silica flour or gas phase
Silica etc.；(3) coupling agent, is usually organo-silicon compound, organic substrate and inorganic filler can be connected to chemical bond
Together；(4) light initiation system, triggers Raolical polymerizable.
Although each of the above component performance last to compound resin all has an impact, influence compound resin mechanical performance and
The predominantly organic substrate of micro.Therefore scientist carries out for the monomer and oligomer of compound resin organic substrate in recent years
Substantial amounts of research.
Bisphenol A-glycidyl Methacrylate (Bis-GMA) is that earliest compound resin monomer occur, and application
Most commonly used monomer.The compound resin that many in the markets occur all is using Bis-GMA as principal monomer, and in clinic
On also show superior performance.And Bis-GMA also there are many deficiencies, it is mainly manifested in：(1) easily water suction, water suction cause multiple
Resin mechanical performance reduces, and reduces the service life of compound resin；(2) double bond conversion rate is not high, and mechanical strength has with conversion ratio
Certain association, in general conversion ratio more high mechanical properties are bigger, and the raising of conversion ratio can reduce unconverted monomer
Leakage；(3) polymerization shrinkage is higher, and polymerization shrinkage can cause to form edge crack between compound resin and tooth body, and finally
Result in marginal microleakage；(4) viscosity is too high, causes the amount for adding filler impacted, have impact on the machine of compound resin accordingly
Tool performance.
Common tooth filling material is silver amalgam, has the spy of strong operability, excellent mechanical performance and wearability
Point.But the color and luster of silver amalgam and tissue of tooth are uncoordinated, and potential Hg toxicity problem just gradually attracts people's attention.
Compound resin as novel mouth repair materials, be it is a kind of by organic resin matrix, inorganic filler and trigger system combinations and
Into teeth repairing material, it has higher mechanical strength, and thermal coefficient of expansion is similar to tooth, insoluble in saliva, color and luster with
The advantages that tooth is close, and it is widely used in the repairing filling of cavity.There is crystal stone for inorganic filler in compound resin
The materials such as English, aerosil, aluminium borate barium disilicate glass.But existing compound resin is still deposited in actual use
In mechanical strength deficiency, wear no resistance, polymerize the shortcomings of volume contraction is larger.
Hydroxyapatite is the host inorganic matter for forming human body hard tissue, it is nontoxic, non-stimulated, without any adverse reaction,
With good biocompatibility and bioactivity, its surface band polarized can be with hydrogen bond with human body cell, polysaccharide and protein
With reference to having stronger affinity with body tissue.Hydroxyapatite can not only play the role of the stent of calcium deposition, and can also
Induce the formation of new bone, directly and human body is soft, sclerous tissues forms bonding can repair and played increasingly in alternate material
Important effect.Nanometer hydroxyapatite can directly close the glaze paint gap formed by demineralization, have good remineralization
Effect.Meanwhile hydroxyapatite crystal also has protein, amino acid, the fat for adsorbing and removing dental surface composition plaque
The effect of the component such as class and glucan.
The performance of compound resin is by the species of inorganic filler, performance, size distribution, the content in resin and resinous substrates
The factor such as combination influence very big, be mainly reflected in physical property and the aspect of mechanical performance two.It is inorganic in existing compound resin
Filler is generally quartz filler, larger with the contact angle of water, and low water absorbable reduces Micro blazed-grating, and resists with stronger surface
Pollution, physical mechanical property are relatively poor.Compound resin there are certain polymerization shrinkage at the same time, and the polymerization of compound resin is received
The border seal of contracting heavy damage dummy, makes the bond failure of Dental Erosion body interface.There is also all for existing preparation method
More limitations, such as：Technique is excessively complicated, and the cycle is longer, poor operability.
Based on background above, shrinking percentage index influences significantly for teeth repairing material in the use of actual dentistry：Tree
Fat contraction is excessive to be caused to directly affect to the mechanical property of material, the prevention of carious tooth, and beauty, do not influencing resin base
In the case of other mechanical strength indexs of body, it is necessary to invent a resin that can ensure low-shrinkage.
The content of the invention
The object of the present invention is to provide a kind of tooth filling renovation material and preparation method thereof.Product uses photocuring tree
Fat, is aided with pre-polymerization resin powder, structure enhancing particle technique (such as nano silicon dioxide or zirconium oxide), at present product
Enhancing technology is using nano silicon dioxide or zirconium oxide is added, and with rapid curing, polishing performance is good, shrinking percentage is low,
The characteristics of mechanical strength is good, wear-resistant, and biocompatibility is excellent, suitable for human teeth I, the tooth filling of II class defects is repaired
Material.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of tooth filling renovation material, including resinous substrates, auxiliary agent, filler and pre-polymerization resin powder；The pre-polymerization
Resin powder is polymerized by Bis-GMA (Bisphenol A-glycidyl Methacrylate).
In above-mentioned tooth filling renovation material, as a kind of preferred embodiment, the pre-polymerization resin powder it is main
Component is Bis-GMA and the first initiator；The reason for pre-polymerization resin powder is added in the tooth filling renovation material is such as
Under：First, the Bis-GMA of a part, the additive amount of opposite reduction Bis-GMA can be replaced；In pre-polymerization resin powder
The Bis-GMA added in Bis-GMA and resinous substrates is a kind of resin, the power of the tooth filling renovation material obtained through the method
Performance is learned to be unaffected；Secondly, the shrinking percentage of tooth filling renovation material can be ensured, and shrinking percentage decreases,
That a part of Bis-GMA of pre-polymerization resin powder first polymerize before resin photocuring use, will not be in resin light with guarantee
Shunk again in solidification process；, can be by this portion furthermore the Bis-GMA resin polymerization conditions in pre-polymerization resin powder are controllable
The mechanical property divided after Bis-GMA monomer polymerizations reaches optimal.The tooth being prepared by above-mentioned batching mode, which is filled, to be repaired
Material, not only increases its mechanical property, and alleviates influence of the shrinkage stress for resin.
Current resin restorative material used on the market uses acrylic acid modified resin more, and Bis-GMA is resin formula
A kind of most important component in the inside, mechanical strength is higher than other acrylic acid modified resins after monomer synthesis, so using
Basic materials of the Bis-GMA as pre-polymerization resin powder.Pre-polymerization resin powder, its polymerization shrinkage are made using Bis-GMA
Had occurred and that in pre-polymerization process, powder autogenous shrinkage rate is very low.It can reduce in resinous substrates part at the same time
The additive amount of Bis-GMA, reduces the shrinking percentage of filling during product use.
In above-mentioned tooth filling renovation material, as a kind of preferred embodiment, in the tooth filling renovation material,
The content of each component is as follows as mass fraction：Resinous substrates 10~20%, auxiliary agent 0.1~0.5%, filler 55~65%, in advance
Polymer resin powder 20~30%；Preferably, resinous substrates 15.7%, auxiliary agent 0.3%, filler 59%, pre-polymerization resin powder
25%.
In above-mentioned tooth filling renovation material, as a kind of preferred embodiment, the tooth filling renovation material is viscous
Thick jelly.
In above-mentioned tooth filling renovation material, as a kind of preferred embodiment, the pre-polymerization resin powder diameter is
0.1~10 μm, the pre-polymerization resin powder diameter is preferably 0.1~1 μm, more preferably 0.4 μm.Pre-polymerization resin powder master
It is the shrinking percentage for reducing tooth filling renovation material to act on.
In above-mentioned tooth filling renovation material, as a kind of preferred embodiment, the resinous substrates are acrylic acid modified
Bisphenol a resin and/or acrylate；Preferably, by mass percentage, in the tooth filling renovation material, institute
The content for stating acrylic acid modified bisphenol a resin is 5-8%, and the content of the acrylate is 5-12%；It is highly preferred that institute
The content 6% of acrylic acid modified bisphenol a resin is stated, the content of the acrylate is 10%.Bisphenol A modified acrylic acid tree
Fat is the Primary resins that current resin realizes mechanical strength, is the main component of current resinous substrates, other modified acroleic acids
Resin is substantially some supplements that some processing aspect deficiency to bisphenol A modified acrylic resin is done.To ensure resin energy
Enough more addition fillers are, it is necessary to add that certain viscosity is relatively low, and processing performance is good, and mechanical strength is unlikely to too again after reaction
The cooperation resin of difference.
In above-mentioned tooth filling renovation material, as a kind of preferred embodiment, the acrylic acid modified bisphenol a resin is
Bisphenol A-glycidyl Methacrylate (Bis-GMA) and/or ethoxylated bisphenol A double methyl methacrylate (Bis-EMA)；
The acrylate is dimethacrylate diisocyanate (UDMA, CAS 72869-86-4, English name
Urethane dimethacrylate) and/or triethylene glycol dimethacrylate (TEG-DMA, CAS 109-16-0, English
Literary fame claims Triethylene glycol dimethacrylate)；It is highly preferred that by mass percentage, filled out in the tooth
Fill in repair materials, the content of the dimethacrylate diisocyanate is 4%, the triethylene glycol dimethacrylate
Content be 6%.
In above-mentioned tooth filling renovation material, as a kind of preferred embodiment, the bisphenol-A in the resinous substrates
Mass fraction of the glycidyl Methacrylate (Bis-GMA) in the tooth filling renovation material is 6%, described
The index of refraction of Bis-GMA is 1.552.
In above-mentioned tooth filling renovation material, as a kind of preferred embodiment, auxiliary agent includes photoinitiator, polymerization triggers
Agent and polymerization inhibitor；It can also include chemical initiator, resin for restoration can be more preferable using light-initiated and chemistry initiation Dual polymerization
Ground ensures mechanical property, in addition adds a certain amount of polymerization inhibitor to ensure to have certain operating time in actual use.It is excellent
Selection of land, mass fraction of the photoinitiator in the tooth filling renovation material are 0.04%, and polymerization initiator is in the tooth
Mass fraction in filling renovation material is 0.25%, and mass fraction of the polymerization inhibitor in the tooth filling renovation material is
0.01%.
In above-mentioned tooth filling renovation material, as a kind of preferred embodiment, the photoinitiator is camphorquinone, cracking
The one or more of type initiator, cationic initiator (such as salt)；Preferably, the photoinitiator is camphorone；It is described
Polymerization inhibitor is preferably to the one or more in hydroxydimethylbenzene, phenols, quinones, arene nitro compound；It is it is highly preferred that described
Polymerization inhibitor is to hydroxydimethylbenzene.The polymerization initiator is one in ETH (isooctyl p-dimethylaminobenzoate), benzene oxygen ketone
Kind or its mixture；It is highly preferred that when polymerization initiator is ETH and benzene oxygen alcohol/ketone mixtures, the ETH is filled in the tooth
Mass fraction in repair materials is 0.18%, and mass fraction of the benzene oxygen ketone in the tooth filling renovation material is
0.07%.
In above-mentioned tooth filling renovation material, as a kind of preferred embodiment, the filler by nanoparticulate fillers and
Glass powder forms；The nanoparticulate fillers are preferably nano-silicon dioxide particle, and the main function of nano silicon dioxide is
Increase the mechanical strength of material；The main function of glass dust mainly increases abrasion resistance, improves optical effect.
It is highly preferred that the nano-silicon dioxide particle particle diameter is one or more of for 10nm, 50nm and 100nm；Further
Ground, mass fraction of nano silicon dioxide that particle diameter is 10nm in the tooth filling renovation material is 3%, particle diameter
It is 6% for mass fraction of the nano-silica powder particle in the tooth filling renovation material of 50nm, particle diameter is
Mass fraction of the nano-silicon dioxide particle of 100nm in the tooth filling renovation material is 3%.Using different grains
The reason for being strengthened after the silica mixing in footpath, is as follows：The less particle reference area of one side particle diameter is larger, individually adds
Add difficult larger and cannot largely add, the excessive shrinking percentage on tooth filling renovation material of additive amount has certain influence；It is another
Aspect is individually unable to reach more preferable wear-resisting and mechanical property again with the larger particle of particle diameter；Therefore, wide in range particle size range pair
In balance, both have certain benefit.
It is highly preferred that the glass powder is particle diameter be 0.4 μm of glass powder and glass powder that particle diameter is 2 μm in
A kind of or its mixture；The reason for using the reason for different-grain diameter glass powder with the silica using different-grain diameter, is identical.
Further, mass fraction of the glass powder that particle diameter is 0.4 μm in the tooth filling renovation material is 40%, grain
Mass fraction of the glass powder that footpath is 2 μm in the tooth filling renovation material is 7%.
The preparation method of above-mentioned tooth filling renovation material, includes the following steps：
It is prepared by pre-polymerization resin powder：Pre-polymerization resin is prepared by solid method in Bis-GMA resins and the first initiator
Powder；
Resinous substrates are mixed with auxiliary agent：Resinous substrates and auxiliary agent are stirred, obtain mixture A；
Mixture A is mixed with filler：Filler is added into said mixture A, is stirred to obtain mixture B；
Mixture B is mixed with pre-polymerization resin powder：Pre-polymerization resin powder is added into said mixture B, stirring is mixed
Conjunction obtains the tooth filling renovation material；
In above-mentioned preparation method, the quality point by each component relative to the raw material total amount of the tooth filling renovation material
Number carries out weighing raw material, wherein, 10~20wt% of resinous substrates, 0.1~0.5wt% of auxiliary agent, 55~65wt% of filler, prepolymerization
20~30wt% of toner.
In above-mentioned preparation method, as a kind of preferred embodiment, in the pre-polymerization resin powder preparation step, institute
It is benzoyl peroxide (BPO), azodiisobutyronitrile (AIBN) etc. to state the first initiator；Preferably, first initiator is
Benzoyl peroxide (BPO), further, the dosage of the benzoyl peroxide are the 0.2% of Bis-GMA resin qualities.
In above-mentioned preparation method, as a kind of preferred embodiment, in the pre-polymerization resin powder preparation step, institute
It is as follows to state solid method preparation condition：Bis-GMA resins are mixed with the first initiator, reaction system is vented 10~20min to vacuum
Spend for -0.05~-0.1Mpa (be preferably -0.1Mpa, i.e. the reading of vacuum meter is -0.1Mpa), 25~55 DEG C are stirred 3~8h,
Then heating polymerization, then post-treated obtain the pre-polymerization resin powder.
It is highly preferred that in the solid method preparation condition, in the heating polymerization, polymerization initiating temperature is 60-70 DEG C, is gathered
The conjunction time is 3~8h.
It is highly preferred that in the solid method preparation condition, the post processing is as follows：Reaction system after polymerization is down to room
Temperature, through circulating crushing, ball milling, drying, sieving, extracting screen underflow is as pre-polymerization resin powder；Further, the circulation crushes
Number is 2~5 times；The Ball-milling Time is 60-120min, is preferably 60min；The drying time is 2~6h, drying temperature
80~120 DEG C；The sieve mesh number of the sieving is 600-1500 mesh.
In above-mentioned preparation method, as a kind of preferred embodiment, in the resinous substrates and auxiliary agent blend step, institute
State resinous substrates to be stirred with photoinitiator, polymerization initiator and polymerization inhibitor, the mixing speed is 3~10r/min, stirring
Time is 20~40min；Preferably, the photoinitiator is camphorquinone, and the polymerization initiator is ETH and/or benzene oxygen ketone, institute
It is to hydroxydimethylbenzene to state polymerization inhibitor.
It is specific in the mixture A and filler blend step as a kind of preferred embodiment in above-mentioned preparation method
Operation is as follows：Nano grade silica particles are added into said mixture A, are stirred, mixing speed is 3~10r/min, when
Between 10~20min；Then add glass dust to be stirred, 3~10r/min of mixing speed, 10~20min of time, is mixed
Thing B.Nano grade silica particles granularity is smaller, preferential in the state of material viscosity is relatively low to add to improve degree of scatter.
In above-mentioned preparation method, as a kind of preferred embodiment, the mixture B is mixed with pre-polymerization resin powder
Step includes successively：Step 1, the pre-polymerization resin powder is added into the mixture B and is stirred, and mixing speed 5~
20r/min, 30~60min of time；Step 2, then continues to stir, 3~10r/min of mixing speed, the time under vacuum
10~20min；Step 3, then finishing reaction system under normal pressure, continue to stir, 5~20r/min of mixing speed, mixing time
30~60min；Step 4, starts again at and vacuumizes and continue to stir, and extremely takes out vacuum in mixing speed 5r/min, 5min
Continue to -0.05~-0.1Mpa and under the conditions of -0.05~-0.1Mpa vacuums (i.e. the reading of vacuum meter) with 15~30r/
Min speed stirs, time 14-16min；Step 5, reverse agitating function under vacuum, 3~10r/min of mixing speed, is stirred
It is 5-10min to mix the time, and stirring finishes to obtain the tooth filling renovation material.
Compared with prior art, technical benefits of the invention is as follows：
The invention discloses a kind of novel tooth filling renovation material and preparation method thereof.With rapid curing, polishability
Can be good, shrinking percentage is low, and mechanical strength is good, wear-resistant, and biocompatibility is excellent the characteristics of, product uses ultraviolet curing process, is aided with
Pre-polymerization resin powder, structure enhancing particle technique, prepares a kind of novel tooth filling renovation material, its cure times is
3-10min, the bending strength after curing are 80-120MPa, and compressive strength 200-300Mpa, shrinking percentage is 1.3~2%, is fitted
Together in tooth I, the reparation of II class defects.Compared to the prior art product mechanics high comprehensive performance of the invention, shrinking percentage is low, fits
For industrial mass production.
Embodiment
A kind of tooth filling renovation material of the present invention and preparation method thereof is illustrated with reference to embodiment.Ying Li
Solution, these embodiments are only used for explaining the present invention rather than limit the scope of the invention.Externally it is to be understood that reading this hair
After bright content, those skilled in the art make various changes or modifications the present invention, and such equivalent forms equally fall within this Shen
Please the appended claims limited range.
Prepare the raw materials used Bis-GMA, UDMA of tooth filling renovation material, TEG-DMA, camphorquinone, ETH, benzene oxygen ketone, right
Hydroxydimethylbenzene, nano-silicon dioxide particle, glass dust, benzoyl peroxide, AIBN etc. belong to commercial goods.
Wherein, the molecular formula of Bis-GMA is shown in formula I：
Molecular weight is 512.59, CAS No.1565-94-2.
Embodiment 1-4
Raw material and inventory are as shown in table 1 used in embodiment 1-4；Wherein, the inventory of each component presses the component
Mass fraction in tooth filling renovation material is calculated.
The preparation method of embodiment 1-4 tooth filling renovation materials is identical, and specific preparation method is as follows：
(1) preparation of pre-polymerization resin powder：Bis-GMA resin monomers and initiator benzoyl peroxide (BPO) is mixed
Close, the dosage of benzoyl peroxide is the 0.2% of Bis-GMA resin qualities, and 50 DEG C of stirrings 5hr, exhaust 15min make its vacuum
For -0.1Mpa.It is poured into after the completion of stirring in pallet, material thickness 10-20mm, and aluminium foil is covered on pallet.Topple over
Cheng Hou, is put into baking oven by pallet and is polymerize, and polymerization initiating temperature is 65 DEG C, polymerization time 5hr.By material temperature after the completion of polymerization
Degree is down to room temperature, and the material being covered on pallet is taken out, is crushed material using jaw crusher, and circulation crushes 3 times.
By the material after crushing on ball mill ball milling mixing 60-120min, after the completion of ball milling, powder is dried, drying time
2hr, 100 DEG C of drying temperature, then crosses the sieve of 1000 mesh, extracting screen underflow is pre-polymerization resin powder, pre-polymerization resin powder
The weight average molecular weight (Wm) at end is 10000-100000.
(2) mixing of resinous substrates and auxiliary agent：Resinous substrates and photoinitiator, polymerization initiator and polymerization inhibitor are filled at the same time
Enter and mixing is stirred in double planetary mixer, 5 revs/min of mixing speed, time 30min, obtains mixture A.
(3) mixing of mixture A and filler：10nm, 50nm, 100nm nano silicon dioxides are added into said mixture A
Particle, 5 revs/min, time 15min of mixing speed, then add 0.4 μm and 2 μm of glass dust, 5 revs/min of mixing speed, when
Between 15min, obtain mixture B.
(4) mixture B and the mixing of pre-polymerization resin powder：Stirred after adding pre-polymerization resin powder into said mixture B
Mix, 10 revs/min of mixing speed, time 40min.Vacuumize, be kept stirring 5 revs/min of speed, stir 15min final finishing trees
Fat, continues to stir, 10 revs/min, time 40min of mixing speed, then vacuumizes, 5 revs/min of mixing speed, it is desirable in 5min
It is evacuated to minimum pressure (- 0.1Mpa) to continue to vacuumize, continues to stir with 20 revs/min of speed under the vacuum, continue to stir
Time is 15 ± 1min；Then, continue to stir in the case where vacuum is 10Pa, but need agitating paddle to invert, 5 revs/min of mixing speed
Clock, mixing time 7min, stirring finish to obtain the tooth filling renovation material.
Mechanics Performance Testing is carried out to above-mentioned teeth repairing material, test result is as shown in table 2.
The constituent table (mass percentage %) of 1 repair materials raw material of table
The performance for the repair materials that 2 each embodiment of table obtains
Claims (10)
1. a kind of tooth filling renovation material, it is characterised in that including resinous substrates, auxiliary agent, filler and pre-polymerization resin powder；
The pre-polymerization resin powder is polymerized by Bis-GMA.
2. tooth filling renovation material according to claim 1, it is characterised in that as mass fraction, the tooth is filled out
Filling repair materials includes following component：Resinous substrates 10~20%, auxiliary agent 0.1~0.5%, filler 55~65%, prepolymerization tree
Cosmetics end 20~30%；Preferably, resinous substrates 15.7%, auxiliary agent 0.3%, filler 59%, pre-polymerization resin powder 25%；It is excellent
Selection of land, the pre-polymerization resin powder diameter are 0.1~1 μm, are preferably 0.4 μm；Preferably, the tooth filling renovation material
For viscous gum.
3. tooth filling renovation material according to claim 1, it is characterised in that the resinous substrates are acrylic acid modified
Bisphenol a resin and/or acrylate；Preferably, by mass percentage, in the tooth filling renovation material, institute
The content for stating acrylic acid modified bisphenol a resin is 5-8%, and the content of the acrylate is 5-12%；It is highly preferred that institute
The content 6% of acrylic acid modified bisphenol a resin is stated, the content of the acrylate is 10%；Further, the propylene
Sour modified bisphenol A resin is Bisphenol A-glycidyl Methacrylate and/or ethoxylated bisphenol A double methyl methacrylate；Institute
It is dimethacrylate diisocyanate and/or triethylene glycol dimethacrylate to state acrylate；It is highly preferred that press
Mass percentage, in the tooth filling renovation material, the content of the dimethacrylate diisocyanate is 4%,
The content of the triethylene glycol dimethacrylate is 6%；More it is highly preferred that bisphenol-A methacrylate shrink is sweet
Mass fraction of the grease in the tooth filling renovation material is 6%.
4. tooth filling renovation material according to claim 1, it is characterised in that auxiliary agent includes photoinitiator, polymerization is drawn
Send out agent and polymerization inhibitor；Preferably, mass fraction of the photoinitiator in the tooth filling renovation material is 0.04%, and polymerization is drawn
It is 0.25% to send out mass fraction of the agent in the tooth filling renovation material, and polymerization inhibitor is in the tooth filling renovation material
Mass fraction be 0.01%；Preferably, the photoinitiator is camphorquinone, cracking type initiator, the one of cationic initiator
Kind is several；It is highly preferred that the photoinitiator is camphorone；The polymerization inhibitor is preferably to hydroxydimethylbenzene, phenols, quinone
Class, arene nitro compound；Further, the polymerization inhibitor is to hydroxydimethylbenzene.The polymerization initiator is ETH, benzene oxygen
One kind or its mixture in ketone；Further, when polymerization initiator is ETH and benzene oxygen alcohol/ketone mixtures, the ETH is described
Mass fraction in tooth filling renovation material is 0.18%, mass fraction of the benzene oxygen ketone in the tooth filling renovation material
For 0.07%.
5. tooth filling renovation material according to claim 1, it is characterised in that the filler by nanoparticulate fillers and
Glass powder forms；The nanoparticulate fillers are preferably nano-silicon dioxide particle；It is highly preferred that the nano silicon dioxide
Particle diameter is one or more of for 10nm, 50nm and 100nm；Further, the nano silicon dioxide that particle diameter is 10nm
Mass fraction in the tooth filling renovation material is 3%, and particle diameter is that the nano-silica powder particle of 50nm exists
Mass fraction in the tooth filling renovation material is 6%, and particle diameter is the nano-silicon dioxide particle of 100nm described
Mass fraction in tooth filling renovation material is 3%；It is highly preferred that the glass powder is the glass dust that particle diameter is 0.4 μm
End and one kind or its mixture in the glass powder that particle diameter is 2 μm；Further, particle diameter is 0.4 μm of the glass powder
Mass fraction in the tooth filling renovation material is 40%, and particle diameter is that 2 μm of the glass powder is filled out in the tooth
The mass fraction filled in repair materials is 7%.
6. according to the preparation method of any one of the claim 1-5 tooth filling renovation materials, it is characterised in that including as follows
Step：
It is prepared by pre-polymerization resin powder：Pre-polymerization resin powder is prepared by solid method in Bis-GMA resins and the first initiator；
Resinous substrates are mixed with auxiliary agent：Resinous substrates and auxiliary agent are stirred by claim 1-5 any proportionings, are obtained
Mixture A；
Mixture A is mixed with filler：Filler is added into said mixture A by any described match of claim 1-5, stirring is mixed
Conjunction obtains mixture B；
Mixture B is mixed with pre-polymerization resin powder：Added by any described match of claim 1-5 into said mixture B
Pre-polymerization resin powder, is stirred to obtain the tooth filling renovation material.
7. preparation method according to claim 6, it is characterised in that in the pre-polymerization resin powder preparation step, institute
It is benzoyl peroxide or azodiisobutyronitrile to state the first initiator；Preferably, first initiator is benzoyl peroxide,
Further, the dosage of the benzoyl peroxide is the 0.2% of Bis-GMA resin qualities；
Preferably, the solid method preparation condition is as follows：Bis-GMA resins are mixed with the first initiator, reaction system exhaust 10
~20min to vacuum be -0.1Mpa, 25~55 DEG C of 3~8h of stirring, then heating polymerization, then it is post-treated obtain it is described pre-
Polymer resin powder；
It is highly preferred that in the solid method preparation condition, in the heating polymerization, polymerization initiating temperature is 60-70 DEG C, during polymerization
Between be 3~8h；
It is highly preferred that in the solid method preparation condition, the post processing is as follows：Reaction system after polymerization is down to room temperature, is passed through
Crushing, ball milling, drying, sieving are circulated, obtains pre-polymerization resin powder；Further, it is 2~5 times that the circulation, which crushes number,；
The Ball-milling Time is 60-120min, is preferably 60min；The drying time is 2~6h, 80~120 DEG C of drying temperature.
8. preparation method according to claim 6, it is characterised in that in the resinous substrates and auxiliary agent blend step, institute
State resinous substrates to be stirred with photoinitiator, polymerization initiator and polymerization inhibitor, the mixing speed is 3~10r/min, stirring
Time is 20~40min.
9. preparation method according to claim 6, it is characterised in that the mixture A is specific with filler blend step
Operation is as follows：Nano grade silica particles are added into said mixture A, are stirred, mixing speed is 3~10r/min, when
Between 10~20min；Then add glass dust to be stirred, 3~10r/min of mixing speed, 10~20min of time, is mixed
Thing B.
10. preparation method according to claim 6, it is characterised in that the mixture B is mixed with pre-polymerization resin powder
Step includes successively：Step 1, the pre-polymerization resin powder is added into the mixture B and is stirred, and mixing speed 5~
20r/min, 30~60min of time；Step 2, then continues to stir, 3~10r/min of mixing speed, the time under vacuum
10~20min；Step 3, then finishing reaction system under normal pressure, continue to stir, 5~20r/min of mixing speed, mixing time
30~60min；Step 4, starts again at and vacuumizes and continue to stir, and extremely takes out vacuum in mixing speed 5r/min, 5min
Continue to stir with 15~30r/min speed to -0.1MPa and under -0.1MPa vacuum degree conditions, time 14-16min；Step
Five, reverse agitating function, 3~10r/min of mixing speed, mixing time 5-10min, stirring under vacuum finishes to obtain described
Tooth filling renovation material.
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| CN2016110708063 | 2016-11-29 | ||
| CN201611070806 | 2016-11-29 |
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